1-(4-alkoxy(or alkylthio)phenyl)-1-(methylenedioxyphenyl)-2-nitroalkanes

ABSTRACT

New Insecticides comprising 1,1-bis(4-substituted phenyl)-2nitropropanes,-2-nitrobutanes and -2-methyl-2-nitropropanes wherein the 4-substituents of the phenyl radicals are nonidentical lower alkoxy groups, or identical or non-identical alkylthio groups, and such compounds wherein one of the 4substituents is replaced by a 3,4-methylene-dioxy group. These compounds are prepared by condensing the appropriate psubstituted-benzaldehyde with the appropriate nitro-alkane and reacting the carbinol product with the appropriately substituted benzene.

United States Patent 91 [111 3,884,938

Holan May 20, 1975 l-(4-ALKOXY(OR ALKYLTHlO)Pl-lENYL)-l-(METHYLENEDIOXYPHENYL)-2- NITROALKANES Inventor: George Holan, Brighton,Australia Assignee: Commonwealth Scientific &

Industrial Research Organization, Campbell, Australia Filed: Dec. 20,1973 Appl. No.: 426,533

Reiated U.S. Application Data Division of Ser. No. 174,265, Aug. 23,1971, Pat. No. 3,823,192.

Foreign Application Priority Data Field of- Search 260/3405 [56]References Cited UNITED STATES PATENTS 3,657,357 4/1972 Holan 260/613 RPrimary Examiner-Lorraine A. Weinberger Assistant Examiner-MichaelShippen Attorney, Agent, or FirmBacon and Thomas [57] ABSTRACT NewInsecticides comprising 1,1-bis(4-substitutedphenyl)-2-nitropropanes,-2-nitrobutanes and -2-methyl- 2-nitropropaneswherein the 4-substituents of the phenyl radicals are non-identicallower alkoxy groups, or identical or non-identical alkylthio groups, andsuch compounds wherein one of the 4-substituents is replaced by a3,4-methylene-dioxy group.

These compounds are prepared by condensing the appropriatep-substituted-benzaldehyde with the appropriate nitro-alkane andreacting the carbinol product with the appropriately substitutedbenzene.

4 Claims, No Drawings Throughout this specification, where the contextpermits, the word insect is used in its broad common usage and includesspiders, mites, nematodes and other pests which are not classed asinsects in the strict biological sense. Thus the term implies referencenot only to those small inverterbrate animals belonging mostly to theclass Insecta, comprising six-legged, usually winged forms, such asbeetles, bugs, flies and the like, but also to other allied classes ofarthropods whose members are Wingless and usually have more than sixlegs, such as spiders, centipedes, wool lice and the like, andespecially to the order Acaridae which includes the mites and ticks. Thewords insecticide and insecticidal are similarly used.

The compounds provided by this invention have the general formula Iwhere R is a methoxy, ethoxy, propoxy, methylthio, ethylthio orpropylthio group and R is hydrogen;

or v

R and R together form a methylenedioxy group (i.e.

o-'cH o-); R is a methoxy, ethoxy, propoxy, methylthio, ethylthio orpropylthio group; with the proviso that R and R are not the same alkoxygroup; and one of the groups R" and R is hydrogen and the other of saidgroups is hydrogen or a methyl group.

The compounds of the invention have substantial insecticidal activity.Against DDT susceptible strains of housefly (Musca domestica), theiractivity is generally at least comparable with that of DDT and relatedinsecticides. The compounds also can be potentiated to high activitylevels even against resistant insect strains. It will be noted that thecompounds contain no halogen and thus their insecticidal activity is ofparticular significance; firstly because the compounds are unlikely togive rise to any residue problems, and secondly, because the normaldetoxification of halogenated insecticides (e.g., DDT) bydehydrochlorination cannot occur, the compounds are active againstinsects which are highly resistant to DDT. Furthermore the compoundsgenerally have a low mammalian toxicity.

Preferred compounds are those in which one of the groups R and R isethoxy, ethylthio or methylenedioxy.

Some preferred individual compounds provided by this aspect of theinvention are:

l-p-ethoxyphenyll -p-methoxyphenyl-2- nitropropane (Ia)l-p-ethoxyphenyll -p-propoxyphenyl-2- nitropropane (lb)l-p-ethoxyphenyll -p-ethylthio-phenyl-2- nitropropane (Ic)l-p-ethoxyphenyll 3 ,4-methylenedioxyphenyl )-2- nitropropane (Id) andthe corresponding 2-nitro-n-butanes (Ic to Ih respectively and2-methyl-2-nitropropanes (Ii to I] respectively).

l-p-ethylthiol 3 ,4-methylenedioxyphenyl )-2- nitropropane and thecorresponding 2-nitro-butane (In) and 2-methyl-2-nitropropane (Io) Knowncompounds related to the compounds I include the dimethoxy analogue ofla, i.e. l,l-bis(pmethoxyphenyl)-2-nitropropane, the unsymmetricaldiethoxy analogue of la i.e.l-o-ethoxyphenyl-l-pethoxyphenyl-2-nitropropane, and the compoundl,lbis(p-ethoxyphenyl)-2-nitroethane, all of which have insignificantinsecticidal activity as shown in the examples herein. The activity ofthe compounds of this invention is generally higher than those of bis(p-ethoxy) compounds which is surprising in view of their assymetricpattern of substitution and their resemblance to known inactivecompounds.

The invention also includes methods for the synthesis of the compounds Idescribed herein, which methods are also applicable to the synthesis ofthe compounds described in our aforementioned copending application.

In accordance with this aspect of the invention, the compounds offormula I are prepared by a method which, in general terms, comprisesthe base catalysed addition of the appropriate nitroalkane with anappropriately substituted benzaldehyde in a suitable solvent to yield acarbinol which is further reacted with the same or another appropriatelysubstituted benzene in the presence of an acid catalyst to give thefinal product.

More specifically in accordance with this aspect of the invention thereis provided a method for the preparation of compounds of the formula I,as stated and defined above, which method comprises the steps of:

a. condensing a benzaldehyde of the formula II where R and R are asdefined above, with a compound of the general formula III wherein R andR are as defined above, the condensation being carried out in a suitablesolvent and in the presence of a basic catalyst; and

b. reacting the carbinol produce resulting from step (a) with a compoundof the formula IV where R is as defined above in the presence of an acidcatalyst.

The procedure may be modified by interchanging the substituents on thebenzene rings of the starting compounds II and IV, e.g., by reacting theappropriate palkoxy or p-alkylthio benzaldehyde with the compound offormula III and then reacting the carbinol product with theappropriately substituted benzene, i.e., carrying the groups R and RApproximately equimolar quantities of the major reactants are generallyused but there may be advantages in employing up to a molar excess ofthe nitro compound III and compound IV.

The solvent/base system for step (a) of the above defined method isselected to satify the general criteria for carbanion-aldehyde typecondensations of nitroaliphatic compounds (the Henry reaction). Theusual systems for such condensations include bases in water, such as thealkaline hydroxides; strong organic bases, such as piperidine or othersecondary or tertiary cyclic or acyclic amines in protonic or aproticsolvents; and alkali metal alkoxides in alcohols or other aprotic orpolar solvents.

However, we have found that care must be taken in selecting suitablesystems as, unless high yields of the carbinol product of step (a) areobtained, the second condensation step (b) may not give the desiredproduct. The process of the present invention appears to be an exceptionto the general applicability of the Henry reaction, asp-ethoxybenzaldehyde and related aldehydes are non-reactive, presumablydue to the stabilization of their structures by resonance. This isreflected in the inability of these compounds to form stable bisulphiteadducts in aqueous solutions. As a result, the usual conditions for theHenry reaction result in extremely poor yields of the carbinols. Forexample, very poor yields result from reactions in water and from theuse of ethanol as solvent with triethylamine, ammonium acetate or sodiummethoxide as basic catalysts. Hence the use of a very strong organictertiary base, such as l,5-diazabicyclo[4.3.0]non-5-ene or 1,5-diazabicyclo[5.4.0]-undec-5-ene, is regarded as essential for successfuloperation of the process of this invention. Selection of the solvent isalso of considerable importance. If ethanol is used the yield of thecarbinol is only about 25% and it is therefore preferred to use asolvent of moderate dielectric strength and weak nucleophilicproperties, such as dimethylsulfoxide, as the solvent. The preferredreaction temperature of this system is from about to C.

In a further aspect the invention also provides general methods for thesynthesis of the symmetrical compounds of formula I, i.e., where thephenyl ring substituents are identical alkylthio groups. In this methodthe 4 appropriate bis-p-(hydroxyphenyl) compound of formula V 5 y @CH YI R c-uo I V R5- en where each of the groups Y is hydroxyl, is reactedwith an N,N-dialkyl-substituted thiocarbamyl chloride (e.g.N,N-dimethylthiocarbamyl chloride) to form the thionocarbamate ester(i.e., formula V; Y OCSN (Alk) where Alk a lower alkyl group).

These esters can be isomerized by heating to form the correspondingthiolocarbamate esters (i.e. formula V; Y SCON(Alk) which in turn arereadily hydrolysed in alkaline solution to give the free thiophenols(i.e., formula V; Y SH). The thiophenols can then be alkylated by anysuitable known procedure, e.g., by reaction with the appropriate dialkylsulphate or alkyl halide. The compounds of formula V where Y OH can beprepared by any suitable method.

The compounds I are insecticidally active against houseflies, mosquitoesand other insects including the sheep blowfly and the Queensland cattletick, both of which are serious pests in Australia. The compounds may beincorporated in a suitable inert solvent, or mixture of solvents, or ina solid mixture with other substances, such as wetting, dispersing andsticking agents. The compounds may be employed in such compositionseither as the sole toxic agent or in combination with otherinsecticides, such as pyrethrum, rotenone, copper salts, etc., or withfungicidal or bactericidal agents, to provide compositions useful forhousehold and agricultural dusts and sprays, textile coating andimpregnation and the like. The compounds may be dissolved in suitableorganic solvents to provide solutions of enhanced utility. The newcompounds may also be placed in aqueous suspension by dispersing organicsolvent solutions of the compounds in water. The new compounds may alsobe mixed with an inert, finely divided, solid diluent or carrier such asbentonite, bole, talc, charcoal, pumice, calcium carbonate and the like.The insecticidal compound may be admixed in its original form or insolution.

In particular, the compounds of the invention may be advantageouslycombined with other substances which have a synergistic or potentiatingaction. Generally such substances are of the class of mixed functionoxidase inhibitors, i.e., they inhibit the detoxification ofinsecticides in insects produced by the action of oxidative enzymes.Typical substances of this tupe are the pyrethrin synergists such aspiperonyl butoxide, piperonyl cyclonene, Sesoxane (sesamex) Sulfoxide,npropyl-isome and sesamine oil extractives. We have found that thesubstance Sesoxane (made by Shulton Inc., Clifton, N..l., USA.) isparticularly useful as a potentiator. (Sesoxane is stated to be2-(3,4-methylenedioxy-phenoxy)-3,6,9,-trioxaudecane). The amount ofSesoxane used may vary from l/lOOOth to five times the weight of thecompound I the preferred range being from about 1/ lOOOth to an equalpart by weight. Piperonyl butoxide also is a useful potentiator insimilar amounts.

It is to be understood that the invention includes all of the abovementioned compositions and other variations thereof as would be evidentto persons skilled in the art. 1

The methods of preparation and the properties of the compounds I areillustrated by the following nonlimiting examples.

EXAMPLE 1.

Preparation of Intermediate nitrocarbinols.

a. 1-( 3 ,4-methylene'dioxyphenyl)-2-nitropropanol.

Piperonal (90 g) was added to nitroethane (90 g) in dry dimethylsulphoxide (180ml). 1,5 Diazabicyclo[4,3,0]-non-5-ene (0.5 g) was added.The mixture was reacted for 16 hrs then sodium bisulphite (110g) inwater (150 ml) was added and stirred for 1 hr. The mixture was quenchedinto water (2 l) and the organic layer was separated and washed withwater. After drying with anhydrous sodium sulphate, residualnitropropane and dimethyl sulphoxide were removed under reducedpressure, yielding a yellow oil 117g.

Analysis Found: C, 51.6; H,4.8; N,6.4.C H NO requires C, 53.5; H, 4.9;N, 6.2

Similarly prepared were:

b. 1-( 3,4-methylenedioxyphenyl)-2-nitrobutanol; from piperonal (90 g)and l-nitropropane (107 g) yield 115 g, MP 9899C. Analysis Found: C,54.8; H, 5,5; N, 5.5. C H NO requires C, 55.2; H, 5.5; N, 5.9.

c. 1-(4-ethoxyphenyl)-2-nitropropanol: from 4- ethoxybenzaldehyde (90 g)and nitroethane (90 g) yield 112 g, MP 6971. Analysis Found: C, 58.8; H,6.7; N, 6.1. C H -NO requires C, 58.7; H, 6.7; N, 6.2

d. 1-(4-ethoxyphenyl)-2-nitrobutanol: from 4- ethoxybenzaldehyde (90 g)and l-nitropropane (107 g) yield 106 g, MP 7880. Analysis "Found: C,60.1; H, 7.1; N, 5.9. C H NQ, requires C, 60.2; H, 7.2; N, 5.9.

EXAMPLE 2.

l -(4-ethoxyphenyl)-1-(4-ethylthiophenyl)-2- nitropropane.

l-(4-ethoxyphenyl)-2-nitropropanol (11.3 g) was added over 1.5 hrs toethyl phenyl sulphide (13. 8 g) in 85% w/w sulphuric acid (50 g)maintained at 5C. The mixture was reacted a further 1.5 hrs thenquenched into ice water (500 ml). The organic layer was separated andwashed with sodium bicarbonate solution and water. After drying withanhydrous sodium sulphate the excess of ethylphenylsulphide was removedunder reduced pressure. The residue was crystallised from ethanol; yield14.7 g, MP 723. Analysis Found: C, 65.7; H, 6.7; N, 4.0; S, 9.1. C I-1 Nrequires C, 66.1; H, 6.7; N, 4.1; S, 9.3.

EXAMPLE 3.

1-( 4-ethoxyphenyl 1 4-ethylthiophenyl)-2- nitrobutane.

l-(4-ethoxyphenyl)-2-nitrobutanol (12 g) was added over 1.5 hrs to ethylphenyl sulphide (13.8 g) in 85% w/w sulphuric acid (50 g) maintained at5C. The mixture was reacted a further 45 minutes then quenched into icewater (500 ml). The organic layer was separated and washed with sodiumbicarbonate solution and water. After drying with anhydrous sodiumsulphate the excess of ethyl phenyl sulphide was removed 6 under reducedpressure. The residue was crystallised from ethanol; yield 15.6 g MP845C. Analysis Found: C, 66.6; H, 7.0; N, 3.6; S, 8.8. C H NO S requiresC, 66.8; H, 7.0; N, 3.9; S, 8.9.

EXAMPLE 4.

l-(4-ethoxyphenyl)-1-(3,4-methylenedioxyphenyl) 2-nitropropane.

1-( 3 ,4-methylenedioxyphenyl )-2-nitropropanol (11.3 g) indichloromethane (20 ml) was added over 1 hr to phenetole (12.2 g) in 85%w/w sulphuric acid maintained, at 0C. The mixture was reacted a further30 minutes then quenched into ice water (500 ml). The organic layer wasseparated and washed with sodium bicarbonate solution and water. Afterdrying with anhydrous sodium sulphate the excess of phenetole wasremoved under reduced pressure. The residue crystallised from ethanol;yield 12.6 g, MP 1 145C. Analysis Found: C, 65.7; H, 5.8; N, 4.0. C H,NO requires C, 65.6; H, 5.8; N, 4.3.

EXAMPLE 5.

1-(4-ethoxyphenyl)-l-(3,4-methylenedioxyphenyl)- 2-nitrobutane.

1-(3,4-methylenedioxyphenyl)-2-nitrobutanol 12 g) in dichloromethane (20ml) was added over 10 minutes to phenetole (12.2 g) in 85% w/w sulphuricacid maintained at -10C. The mixture was reacted on additional 50minutes then quenched into ice water (500 ml). The organic layer wasseparated and washed with sodium bicarbonate solution and water. Afterdrying with anhydrous sodium sulphate the excess phenetole was removedunder reduced pressure. The residue was crystallised from ethanol; yield13.4 g, MP l00-lC. Analysis Found: C, 66.2; H, 6.2; N, 3.8. C H NOrequires C, 66.5; H, 6.2; N, 4.1.

EXAMPLE 6.

l-(4-ethoxyphenyl l 4-methoxyphenyl )-2- nitrobutane.

1-(4-ethoxyphenyl)-2-nitrobutanol (3.6 g) was added over 30 minutes toanisole (3.24 g) in 85% sulphuric acid (7.5 mls) maintained at 05C withvigorous stirring. The mixture was reacted an additional 30 minutes andthen quenched into ice-water ml). The organic layer was separated,washed with sodium bicarbonate solution and water and dried withanhydrous sodium sulphate. The solution was evaporated to dryness toyield, on crystallisation from ethanol, the product as crystals, meltingat 93C.

EXAMPLE 7.

l-p-ethylthiophenyll 3 ,4-methylenedioxy-phenyl )-2- nitroprop ane.

1 1.3 g of l-(3,4-methylenedioxyphenyl)-2- nitropropanol was dissolvedin 20g of ethylthiobenzene and added over 1 hour to 50 g of sulphuricacid cooled in an ice bath. The mixture was stirred for a further 2.5hours and then quenched into 500 ml ice water. The organic layer wasseparated and washed with sodium bicarbonate solution and water. Theresidual oil was dried over sodium sulphate and then under vacuum andchromatographed in benzene over silica gel. Crystallisation frombenzene/petroleum ether (b.p. 50 80C) gave 4.9 g ofl-p-ethylthiophenyl-l- EXAMPLE 8.

l-p-ethylthiophenyll 3,4-methylenedioxyphcnyl Z-nitrobutane.

l-( 3 ,4-methylenedioxyphenyl)-2-nitrobutanol (12 g) was dissolved inwarm ethylthiobenzene (200g) and added over 1 hour to 85% sulphuric acid(50g) maintained at C. The mixture was stirred for a further 2 hours andthen quenched into ice water (500 ml.). The product was worked up as inExample 7 to yield 6.6 g crystals melting at 60C.

In all of the above examples NMR, IR and mass spectra were consistentwith the named products.

The improved method of the invention is further illustrated by thefollowing Examples, which show the large scale preparation of thecompounds of our aforesaid copending application.

EXAMPLE 9 a. Preparation of l-p-ethoxyphenyl-2-nitrobutan-1- ol.

p-Ethoxybenzaldehyde (450g) and l-nitropropane (535g) were dissolved in900 ml of dimethyl sulphoxide containing 2.5g ofl,5-diazabicyclo[4,3,0]non--ene and the mixture stirred at roomtemperature for hours. The mixture was then poured into ice and, aftrether extraction, yielded an oil containingl-p-ethoxyphenyl-2-nitrobutan-1-ol. The infra-red spectrum of theproduct indicated the presence of about 15% by weight of the aldehydestating material.

b. Purification of the carbinol The impure product obtained as above wasmixed with 450g of sodium metabisulphite to which 43 ml of water hadbeen added. The solid was allowed to separate and the liquid phasedecanted off and similarly treated with two further 450g amounts of themetabisulphite (plus water) over a total period of about 3 hours. Theliquid product was then filtered or decanted. The IR spectrum thenshowed no carbonyl absorption at 1,680 cm and the product was consideredaldehyde-free.

Crystallization from petroleum ether yielded crystals of the carbinolm.p. 62C. IR and NMR spectrum confirmed the structure of the product asl-p-ethoxyphenyl-2-nitrobutan-1-0l. The yield was 493g (68.8% oftheoretical).

c. Preparation of 1,1-bis(p-ethoxypheny1)-2-nitro-nbutane.

The pure carbinol product obtained as above was added over 1V2 hours toa reaction mixture consisting 488g of phenetole in 950 ml of 85%sulphuric acid at 05C. After a further two hours the mixture wasquenched in ice and extracted with ether. The ether extract onevaporation gave a residue which was crystallized from ethanol to give1,l-bis(p-ethoxyphenyl)-2- nitro-n-butane as a stable crystalline soldm.p. 82C. The identity of the product was confirmed by molecular weight,IR and NMR. The yield was 75.5% of theory which represents an overallyield of 52% for the threestage process.

EXAMPLE 10. Preparation of 1,1-bis(p-ethoxyphenyl)-2-nitrobutane fromunpurified carbinol.

l-p-ethoxyphenyl-2-nitrobutan-l-ol was prepared as in the above example.510g of the product, which was estimated by IR to be -75% pure, wasadded over two hours to a solution of phenetole (366g) in H,SO (1200 ml)keeping the temperature between 5 and 10C. After stirring a furtherhour,the mixture was quenched and the product isolated. The product (852g)was mainly polymer, as indicated by NMR, with no biological activity.

EXAMPLE 1 1 Using the method described in Example 9,l-pethoxy-phenyl-2-nitropropan-l-ol was prepared fromp-ethoxy-benzaldehyde and nitroethane, purified and reacted withphenetole to give l,l-bis(pethoxyphenyl)-2-nitropropane. Similar yieldswere obtained throughout and the product was a stable oil b.p. C at 10Torr., identified by molecular weight, IR and NMR.

EXAMPLE 12 Preparation of 1,1-bis( p-ethoxyphenyl)-2-nitropropanewithout purification of the intermediate carbinol:

p-ethoxybenzaldehyde (450g) and nitroethane (450g) were added to 800 mlsof dimethylsulphoxide containing l,5-diazabicyclo[4,3,0]non-5-ene (1.5g)and stirred overnight. The mixture was quenched into 1 l. of water,separated with methylene dichloride and after washing with water thecarbinol (671 g) was recovered by evaporation as an oil. A mixture ofphenetole (732g) in 85% sulphuric acid (2,400 ml) was cooled to 10C andthe unpurified carbinol (670g) was added over 2 hours. The mixture wasstirred for a further two hours and quenched into ice water. The solidproduct obtained corresponded to about an 80% yield. However, NMRexamination indicated that it contained at least 70% of a polymericmaterial and its insecticidal testing showed no biological activity.

EXAMPLE 13 The procedure of Example 9 was repeated except thatpurification of the carbinol was effected by mixing with hydrazinehydrate in an amount equivalent to the amount of aldehyde present (foundfrom the IR spectrum). After filtering off the solid azine formed, thepurified carbinol was reacted with phenetole. A stable crystallineproduct was again obtained, the yields being similar to those in Example9.

EXAMPLE l4.

1-(4-ethylthiophenyl l 4-methoxyphenyl)-2- nitrobutane.

The carbinol l-(4-methoxyphenyl)-2nitrobutanol was prepared according tothe method of Example 1 from 4-methoxybenzaldehyde (81 g) andnitropropane (107 g). The product was obtained as crystals m.p. 68-9C;yield 86%.

The carbinol (11.25 g) was dissolved in a mixture of ethylphenylsulphide(13.8 g) and dichloromethane (10 ml) and the mixture added during 1 hourto a vigorously-stirred mixture of sulphuric acid (45 g) and water (5 g)in an ice bath. After a further 2 hours stirring the mixture was pouredinto 500 ml of ice water and oily phase separated. The aqueous phase wasextracted with dichlormethane (2 X 25 ml) and the extracts were combinedwith the oily phase and washed with sodium bicarbonate solution (100ml). The extract was dried over anhydrous sodium sulphate and thesolvent and excess thioether removed by heating at 60/0.l mm Hg for 1hour. The residue was crystallised from 96% ethanol, to give thecrystalline product, mp 78- yield 84%.

EXAMPLE l5 Insecticidal Activity The following tests method was used todetermine the activities of the compounds of the foregoing Examples.

Tests were carried out on the common housefly, using a standardDDT-susceptible strain (WHO/INI- Musca domestica/l The compound wasapplied in an acetone solution by microsyringe to the dorsum of thethorax of two day old female flies reared from pupae of average weight2.2 2.5 gm/lOO pupae. The adult flies were fed on water and sugar-onlydiet and maintained at 26C and 70% RH. The mortalities were counted at48 hours after treatment and compared with acetonetreated controls.Flies unable to move or stand normally were considered dead. The LDvalues obtained from a logit computer programme based on threereplicates of flies at each dose level are given in Table 1.

Potentiation The above compounds were also tested on the insectsdescribed above in conjunction with the potentiator Sesoxane by applying0.5 microlitres of 1% w/w acetone solution of Sesoxane with the compoundunder test.

The mortalities were counted at 48 hours after treatment and comparedwith acetone and acetone/potentiator controls.

The LD values were determined as described above and the results arealso given in Table 1.

TABLE 1 Compound of Examples LD values (pg/insect) Figures given forcomparison for (a) 1,l-bis(p-ethoxypheny1) Z-nitropropane; (b) l.1-bis(p-ethoxyphenyl)-2-nitro butane; (c)1.1-bis(p-methoxyphenyl)-2-nltropropane;1-(o-ethoxypheny1)-1-(p'ethoxyphenyl)-2-nitropropane;1,1-bis(p-ethoxypheny1)-2-nitroethane; and DDT.)

EXAMPLE 16 The following are examples of insecticidal compositions inaccordance with the invention. All parts are by weight.

a. Spray formulation The following composition is adapted for sprayapplication.

Compound of formula 1 4.0 Sesoxane or Piperonyl butoxide 1.0 Deodorizedkerosene 79.4 Alkylated napthalene 16.0

b. Aerosol The following materials are metered into a suitable bombcontainer sealed and equipped with a valve in the usual way.

Compound of formula I 3.0 Potentiator l .0 Methylene chloride 10.0 Freon12 43.0 Freon 11 43.0

It will be appreciated that modifications may be made to the process ofour invention as specifically described above, and it is to beunderstood that the invention includes all such modifications which fallwithin its spirit and scope.

I claim:

1. A compound of the formula:

R alt wherein R and R together form a methylenedioxy group; R is amethoxy, ethoxy, propoxy, methylthio, ethylthio or propylthio group; andone of the groups R and R is hydrogen and the other of said groups ishydrogen or a methyl group.

2. 1-p-ethoxyphenyl-1-(3 ,4-methylenedioxyphenyl)- 2-nitro-butane 3.l-p-ethylthiopheny1-1-(3 ,4- methylenedioxyphenyl)-2-nitropropane.

1-p-ethylthiophenyl-1-(3 ,4-methylenedioxyphenyl)-2-nitro-butane UNITEDSTATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO.3 4 3 DATED May 20, 1975 |N\/ ENTOR(S) George Holan It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Col. 1,

insert --August 31, 1970 Australia 2367/70-- Signed and Scaled thistwenty-sixth Day 0f August 1975 [SEAL] Attest:

RUTH C. MASON Arresting Officer C. MARSHALL DANN Commissioner of Parentsand Trademarks UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OFCORRECTION PATENT NO. 3 4 3 DATED May 20, 1975 lN\/ ENTOR(S) GeorgeHolan It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

Col. 1, first line beneath Foreign Application Priority Data insert--August 31, 1970 Australia 2367/70-- Signed and Scaled thistwenty-sixth Day of August 1975 [SEAL] A ttes t:

RUTH C. MASON Arresting Officer C. MARSHALL DANN Commissioner of Parentsand Trademarkx

1. A COMPOUND OF THE FORMULA:
 2. 1-p-ethoxyphenyl-1-(3,4-methylenedioxyphenyl)-2-nitro-butane
 3. 1-p-ethylthiophenyl-1-(3,4-methylenedioxyphenyl)-2-nitropropane.
 4. 1-p-ethylthiophenyl-1-(3,4-methylenedioxyphenyl)-2-nitro-butane 